Two types of distribution for α C values are observed in anaerobic environments when δ 13C–ΣCO 2 and δ 13C–CH 4 values are measured across gradients of depth or age of organic debris. The type-I distribution involves a systematic increase in α C values with depth as a result of decreasing δ 13C–CH 4 and increasing δ 13C–ΣCO 2 values. This behavior corresponds to a progressive increase in the prevalence of methanogenesis by the CO 2 reduction pathway relative to acetate fermentation. Utilization of autotrophically formed acetate by methanogens would also cause an increase in α C values. The type-II distribution occurs when both δ 13C–CH 4 and δ 13C–ΣCO 2 values decrease with depth, resulting in approximately constant α C values. This condition corresponds with a strong dependence of methanogens on porewater ΣCO 2 as a carbon source by way of either the CO 2 reduction pathway or utilization of autotrophically formed acetate. Freshwater wetlands possess both types of α C value distribution. Wetlands with type-I distributions exhibit curves with slopes that vary probably as a function of deposition and preservation of labile organic carbon. An abundance of labile substrates in anaerobic soils yields steeper curves because aceticlastic methanogenesis predominates and δ 13C–CH 4 and δ 13C–CO 2 values are high. Diminished transfer of labile carbon to the methanogenic zone results in an increased prevalence of the CO 2 reduction pathway, yielding low δ 13C–CH 4 values and shallowly sloping curves. Aerobic oxidation of organic matter or decay involving sulfate reduction produces CO 2 with low δ 13C values, which also will contribute to shallowly sloping curves. The size of the dissolved CO 2 pool can influence the sensitivity of δ 13C–CO 2 values to change during methanogenesis. Regression curves of δ 13C–CH 4 and δ 13C–ΣCO 2 values from four wetlands with type-I distributions intersect at δ 13C–CH 4 = −40.7 ± 6.1‰ (1σ) and δ 13C–ΣCO 2 = −23.9 ± 4.8‰ (1σ). These values are similar to δ 13C values for methyl and carboxyl moieties within acetate produced by anaerobic degradation of fresh C 3 plant matter. A low abundance of acetate during aceticlastic methanogenesis will result in minimal expression of metabolic kinetic isotope effects (KIEs) and production of CH 4 and CO 2 with δ 13C values similar to the intramolecular distribution of sedimentary acetate. The type-II distribution is prevalent in marine environments, probably because of substrate depletion in the sulfate reduction zone. The type-I distribution does occur in marine settings where deposition rates of organic matter are high. Landfills possess only the type-I distribution of α C values and exhibit unusually steep curves, possibly because methanogenesis occurs predominantly from acetate produced by fermentation at mesophilic temperatures. The high abundance of acetate in landfill leachate may permit varying degrees of expression of the KIE associated with aceticlastic methanogenesis. Outgassing of 12CO 2 may contribute further to the steepening of α C curves in landfills and other anaerobic environments possessing a type-I distribution. Defining the type of α C distributions in different wetlands could reduce uncertainty in estimating the δ 13C value of CH 4 emissions. Hence, the prevalence of type-I vs. type-II α C distributions in wetlands may have practical importance for the refinement of global CH 4 budgets that rely on 13C/ 12C ratios for mass balance.